Carbon management and sequestration from encapsulated control infrastructures

ABSTRACT

A method of sequestering carbon dioxide emissions during recovery of hydrocarbons from hydrocarbonaceous materials can include forming a constructed permeability control infrastructure. This constructed infrastructure defines a substantially encapsulated volume. A comminuted hydrocarbonaceous material can be introduced into the control infrastructure to form a permeable body of hydrocarbonaceous material. The permeable body can be heated sufficient to remove hydrocarbons therefrom. During heating, the hydrocarbonaceous material is substantially stationary as the constructed infrastructure is a fixed structure. Additionally, during heating, any carbon dioxide that is produced can be sequestered. Removed hydrocarbons can be collected for further processing, use in the process, and/or use as recovered.

RELATED APPLICATION

This application claims priority to U.S. Provisional Patent ApplicationNo. 61/152,220 filed Feb. 12, 2009 which is incorporated herein byreference.

BACKGROUND

Global and domestic demand for fossil fuels continues to rise despiteprice increases and other economic and geopolitical concerns. As suchdemand continues to rise, research and investigation into findingadditional economically viable sources of fossil fuels correspondinglyincreases. Historically, many have recognized the vast quantities ofenergy stored in oil shale, coal and tar sand deposits, for example.However, these sources remain a difficult challenge in terms ofeconomically competitive recovery. Canadian tar sands have shown thatsuch efforts can be fruitful, although many challenges still remain,including environmental impact, product quality, production costs andprocess time, among others.

Estimates of world-wide oil shale reserves range from two to almostseven trillion barrels of oil, depending on the estimating source.Regardless, these reserves represent a tremendous volume and remain asubstantially untapped resource. A large number of companies andinvestigators continue to study and test methods of recovering oil fromsuch reserves. In the oil shale industry, methods of extraction haveincluded underground rubble chimneys created by explosions, in-situmethods such as In-Situ Conversion Process (ICP) method (Shell Oil), andheating within steel fabricated retorts. Other methods have includedin-situ radio frequency methods (microwaves), and “modified” in-situprocesses wherein underground mining, blasting and retorting have beencombined to make rubble out of a formation to allow for better heattransfer and product removal.

Among typical oil shale processes, all face tradeoffs in economics andenvironmental concerns. No current process alone satisfies economic,environmental, and technical challenges. Moreover, global warmingconcerns give rise to additional measures to address carbon dioxide(CO₂) emissions which are associated with such processes. Methods areneeded that accomplish environmental stewardship, yet still providehigh-volume cost-effective oil production.

Below ground in-situ concepts emerged based on their ability to producehigh volumes while avoiding the cost of mining. While the cost savingsresulting from avoiding mining can be achieved, the in-situ methodrequires heating a formation for a longer period of time due to theextremely low thermal conductivity and high specific heat of solid oilshale. Perhaps the most significant challenge for any in-situ process isthe uncertainty and long term potential of water contamination that canoccur with underground freshwater aquifers. In the case of Shell's ICPmethod, a “freeze wall” is used as a barrier to keep separation betweenaquifers and an underground treatment area. Although this is possible,no long term analysis has proven for extended periods to guarantee theprevention of contamination. Without guarantees and with even fewerremedies should a freeze wall fail, other methods are desirable toaddress such environmental risks.

For this and other reasons, the need remains for methods and systemswhich can provide improved recovery of hydrocarbons from suitablehydrocarbon-containing materials, which have acceptable economics andavoid the drawbacks mentioned above.

SUMMARY

A method of recovering hydrocarbons from hydrocarbonaceous materials caninclude forming a constructed permeability control infrastructure. Thisconstructed infrastructure defines a substantially encapsulated volume.A mined hydrocarbonaceous material can be introduced into the controlinfrastructure to form a permeable body of hydrocarbonaceous material.The permeable body can be heated sufficient to remove hydrocarbonstherefrom. During heating the hydrocarbonaceous material can besubstantially stationary. Additionally, during heating, any carbondioxide that is produced can be sequestered. Removed hydrocarbons can becollected for further processing, use in the process as supplementalfuel or additives, and/or direct use without further treatment.

Additional features and advantages of these principles will be apparentfrom the following detailed description, which illustrates, by way ofexample, features of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is side partial cutaway view schematic of a constructedpermeability control infrastructure in accordance with one embodiment.

FIGS. 2A and 2B are top and plan views of a plurality of permeabilitycontrol impoundments in accordance with one embodiment.

FIG. 3 is a side cutaway view of a permeability control impoundment inaccordance with one embodiment.

FIG. 4 is a schematic of a portion of a constructed infrastructure inaccordance with an embodiment.

FIG. 5 is a schematic showing heat transfer between two permeabilitycontrol impoundments in accordance with another embodiment.

It should be noted that the figures are merely exemplary of severalembodiments and no limitations on the scope of the present invention areintended thereby. Further, the figures are generally not drawn to scale,but are drafted for purposes of convenience and clarity in illustratingvarious aspects of the invention.

DETAILED DESCRIPTION

Reference will now be made to exemplary embodiments and specificlanguage will be used herein to describe the same. It will neverthelessbe understood that no limitation of the scope of the invention isthereby intended. Alterations and further modifications of the inventivefeatures described herein, and additional applications of the principlesof the invention as described herein, which would occur to one skilledin the relevant art and having possession of this disclosure, are to beconsidered within the scope of the invention. Further, before particularembodiments are disclosed and described, it is to be understood thatthis invention is not limited to the particular process and materialsdisclosed herein as such may vary to some degree. It is also to beunderstood that the terminology used herein is used for the purpose ofdescribing particular embodiments only and is not intended to belimiting, as the scope of the present invention will be defined only bythe appended claims and equivalents thereof.

DEFINITIONS

In describing and claiming the present invention, the followingterminology will be used.

The singular forms “a,” “an,” and “the” include plural references unlessthe context clearly dictates otherwise. Thus, for example, reference to“a wall” includes reference to one or more of such structures, “apermeable body” includes reference to one or more of such materials, and“a heating step” refers to one or more of such steps.

As used herein “existing grade” or similar terminology refers to thegrade or a plane parallel to the local surface topography of a sitecontaining an infrastructure as described herein which infrastructuremay be above or below the existing grade.

As used herein, “conduits” refers to any passageway along a specifieddistance which can be used to transport materials and/or heat from onepoint to another point. Although conduits can generally be circularpipes, other non-circular conduits can also be useful. Conduits canadvantageously be used to either introduce fluids into or extract fluidsfrom the permeable body, convey heat transfer, and/or to transport radiofrequency devices, fuel cell mechanisms, resistance heaters, or otherdevices.

As used herein, “constructed infrastructure” refers to a structure whichis substantially entirely man made, as opposed to freeze walls, sulfurwalls, or other barriers which are formed by modification or fillingpores of an existing geological formation.

The constructed permeability control infrastructure is oftensubstantially free of undisturbed geological formations, although theinfrastructure can be formed adjacent or in direct contact with anundisturbed formation. Such a control infrastructure can be unattachedor affixed to an undisturbed formation by mechanical means, chemicalmeans, or a combination of such means, e.g. bolted into the formationusing anchors, ties, or other suitable hardware.

As used herein, “comminuted” refers to breaking a formation or largermass into pieces. A comminuted mass can be rubbilized or otherwisebroken into fragments.

As used herein, “hydrocarbonaceous material” refers to anyhydrocarbon-containing material from which hydrocarbon products can beextracted or derived. For example, hydrocarbons may be extracteddirectly as a liquid, removed via solvent extraction, directly vaporizedor otherwise removed from the material. However, many hydro carbonaceousmaterials contain kerogen or bitumen which is converted to a hydrocarbonthrough heating and pyrolysis. Hydrocarbonaceous materials can include,but is not limited to, oil shale, tar sands, coal, lignite, bitumen,peat, and other organic materials.

As used herein, “impoundment” refers to a structure designed to hold orretain an accumulation of fluid and/or solid moveable materials. Animpoundment generally derives at least a substantial portion offoundation and structural support from earthen materials. Thus, thecontrol walls do not always have independent strength or structuralintegrity apart from the earthen material and/or formation against whichthey are formed.

As used herein, “permeable body” refers to any mass of comminuted hydrocarbonaceous material having a relatively high permeability whichexceeds permeability of a solid undisturbed formation of the samecomposition. Suitable permeable bodies can have greater than about 10%void space and typically have void space from about 30% to 45%, althoughother ranges may be suitable. Allowing for high permeabilityfacilitates, for example, through the incorporation of large irregularlyshaped particles, heating of the body through convection as the primaryheat transfer while also substantially reducing costs associated withcrushing to very small sizes, e.g. below about 1 to about 0.5 inch.

As used herein, “wall” refers to any constructed feature having apermeability control contribution to confining material within anencapsulated volume defined at least in part by control walls. Walls canbe oriented in any manner such as vertical, although ceilings, floors,and other contours defining the encapsulated volume can also be “walls”as used herein.

As used herein, “mined” refers to a material which has been removed ordisturbed from an original stratographic or geological location to asecond and different location or returned to the same location.Typically, mined material can be produced by rubbilizing, crushing,explosively detonating, or otherwise removing material from a geologicformation.

As used herein, “adsorb,” “adsorbing,” or “adsorbed” refers to theprocess where a gas or liquid solute accumulates on the surface of asolid or a liquid or diffuses into a solid or liquid. Generally, whenreferring to carbon dioxide, the carbon dioxide is adsorbed into amaterial such that the carbon dioxide is substantially immobilized.

As used herein, “substantially stationary” refers to nearly stationarypositioning of materials with a degree of allowance for subsidence,expansion, and/or settling as hydrocarbons are removed from thehydrocarbonaceous material from within the enclosed volume to leavebehind lean material. In contrast, any circulation and/or flow ofhydrocarbonaceous material such as that found in fluidized beds orrotating retorts involves highly substantial movement and handling ofhydrocarbonaceous material.

As used herein, “substantial” when used in reference to a quantity oramount of a material, or a specific characteristic thereof, refers to anamount that is sufficient to provide an effect that the material orcharacteristic was intended to provide. The exact degree of deviationallowable may in some cases depend on the specific context. Similarly,“substantially free of” or the like refers to the lack of an identifiedelement or agent in a composition. Particularly, elements that areidentified as being “substantially free of” are either completely absentfrom the composition, or are included only in amounts which are smallenough so as to have no measurable effect on the composition.

As used herein, “about” refers to a degree of deviation based onexperimental error typical for the particular property identified. Thelatitude provided the term “about” will depend on the specific contextand particular property and can be readily discerned by those skilled inthe art. The term “about” is not intended to either expand or limit thedegree of equivalents which may otherwise be afforded a particularvalue. Further, unless otherwise stated, the term “about” shallexpressly include “exactly,” consistent with the discussion belowregarding ranges and numerical data.

Concentrations, dimensions, amounts, and other numerical data may bepresented herein in a range format. It is to be understood that suchrange format is used merely for convenience and brevity and should beinterpreted flexibly to include not only the numerical values explicitlyrecited as the limits of the range, but also to include all theindividual numerical values or sub-ranges encompassed within that rangeas if each numerical value and sub-range is explicitly recited. Forexample, a range of about 1 to about 200 should be interpreted toinclude not only the explicitly recited limits of 1 and 200, but also toinclude individual sizes such as 2, 3, 4, and sub-ranges such as 10 to50, 20 to 100, etc.

As used herein, a plurality of items, structural elements, compositionalelements, and/or materials may be presented in a common list forconvenience. However, these lists should be construed as though eachmember of the list is individually identified as a separate and uniquemember. Thus, no individual member of such list should be construed as ade facto equivalent of any other member of the same list solely based ontheir presentation in a common group without indications to thecontrary.

Carbon Management and Sequestration from Control Infrastructures

A method of recovering hydrocarbons from hydrocarbonaceous materials caninclude forming a constructed permeability control infrastructure. Thisconstructed infrastructure defines a substantially encapsulated volume.A mined or harvested hydro carbonaceous material can be introduced intothe control infrastructure to form a permeable body of hydrocarbonaceousmaterial. The permeable body can be heated sufficient to removehydrocarbons therefrom. During heating, the hydrocarbonaceous materialis substantially stationary as the constructed infrastructure is a fixedstructure. Additionally, during heating, at least a portion of carbondioxide that is produced can be sequestered. Removed fluid hydrocarbonscan be collected for further processing, use in the process, and/or useas recovered.

The constructed permeability control infrastructure can be formed usingexisting grade as floor support and/or as side wall support for theconstructed infrastructure. For example, the control infrastructure canbe formed as a free standing structure, i.e. using only existing gradeas a floor with side walls being man-made. Alternatively, the controlinfrastructure can be formed within an excavated pit. Regardless, thecontrol infrastructures are always formed above-grade.

A constructed permeability control infrastructure can include apermeability control impoundment which defines a substantiallyencapsulated volume. The permeability control impoundment issubstantially free of undisturbed geological formations. Specifically,the permeability control aspect of the impoundment can be completelyconstructed and manmade as a separate isolation mechanism for preventionof uncontrolled migration of material into or out of the encapsulatedvolume.

In one embodiment, the permeability control impoundment can be formedalong walls of an excavated hydrocarbonaceous material deposit. Forexample, oil shale, tar sands, or coal can be mined from a deposit toform a cavity which corresponds approximately to a desired encapsulationvolume for an impoundment. The excavated cavity can then be used as aform and support to create the permeability control impoundment.

In one alternative aspect, at least one additional excavatedhydrocarbonaceous material deposit can be formed such that a pluralityof impoundments can be operated. Further, such a configuration canfacilitate a reduction in transportation distance of the mined material.Specifically, the mined hydro carbonaceous material for any particularencapsulated volume can be mined from an adjacent excavatedhydrocarbonaceous material deposit. In this manner, a grid ofconstructed structures can be built such that mined material can beimmediately and directly filled into an adjacent impoundment.

Mining and/or excavation of hydrocarbonaceous deposits can beaccomplished using any suitable technique. Conventional surface miningcan be used, although alternative excavators can also be used withoutrequirement of transportation of the mined materials. In one specificembodiment, the hydrocarbonaceous deposit can be excavated using acrane-suspended excavator. One example of a suitable excavator caninclude vertical tunnel boring machines. Such machines can be configuredto excavate rock and material beneath the excavator. As material isremoved, the excavator is lowered to ensure substantially continuouscontact with a formation. Removed material can be conveyed out of theexcavation area using conveyors or lifts. Alternatively, the excavationcan occur under aqueous slurry conditions to reduce dust problems andact as a lubricant/coolant. The slurry material can be pumped out of theexcavation for separation of solids in a settling tank or other similarsolid-liquid separator, or the solids may be allowed to precipitatedirectly in an impoundment. This approach can be readily integrated withsimultaneous or sequential solution-based recovery of metals and othermaterials as described in more detail below.

Further, excavation and formation of a permeability control impoundmentcan be accomplished simultaneously. For example, an excavator can beconfigured to remove hydrocarbonaceous material while side walls of animpoundment are formed. Material can be removed from just underneathedges of the side walls such that the walls can be guided downward toallow additional wall segments to be stacked above. This approach canallow for increased depths while avoiding or reducing dangers of cave-inprior to formation of supporting impoundment walls.

The impoundment can be formed of any suitable material which providesisolation of material transfer across walls of the impoundment. In thismanner, integrity of the walls is retained during operation of thecontrol infrastructure sufficient to substantially prevent uncontrolledmigration of fluids outside of the control infrastructure. Non-limitingexamples of suitable material for use in forming the impoundment of theconstructed permeability control infrastructure can include clay,bentonite clay (e.g. clay comprising at least a portion of bentonite),bentonite amended soil, compacted fill, refractory cement, cement,synthetic geogrids, fiberglass, rebar, nanocarbon fullerene additives,filled geotextile bags, polymeric resins, oil resistant PVC liners, orcombinations thereof. Engineered cementitious composites (ECC)materials, fiber reinforced composites, and the like can be particularlystrong and can be readily engineered to meet permeability andtemperature tolerance requirements of a given installation. As a generalguideline, materials having low permeability and high mechanicalintegrity at operating temperatures of the infrastructure can providegood performance, although are not required. For example, materialshaving a melting point above the maximum operating temperature of theinfrastructure can be useful to maintain containment during and afterheating and recovery. However, lower temperature materials can also beused if a non-heated buffer zone is maintained between the walls andheated portions of the permeable body. Such buffer zones can range from6 inches to 50 feet depending on the particular material used for theimpoundment and the composition of the permeable body. In anotheraspect, walls of the impoundment can be acid, water, and/or brineresistant, e.g. sufficient to withstand exposure to solvent recoveryand/or rinsing with acidic or brine solutions, as well as to steam orwater. For impoundment walls formed along formations or other solidsupport, the impoundment walls can be formed of a sprayed grouting,sprayed liquid emulsions, or other sprayed material such as sprayablerefractory grade grouting which forms a seal against the formation andcreates the permeability control wall of the impoundments. Impoundmentwalls may be substantially continuous such that the impoundment definesthe encapsulated volume sufficiently to prevent substantial movement offluids into or out of the impoundment other than defined inlets andoutlets, e.g. via conduits or the like as discussed herein. In thismanner, the impoundments can readily meet government fluid migrationregulations. Alternatively, or in combination with a manufacturedbarrier, portions of the impoundment walls can be undisturbed geologicalformation and/or compacted earth. In such cases, the constructedpermeability control infrastructure is a combination of permeable andimpermeable walls as described in more detail below.

In one detailed aspect, a portion of hydro carbonaceous material, eitherpre- or post-processed, can be used as a cement fortification and/orcement base which are then poured in place to form portions or theentirety of walls of the control infrastructure. These materials can beformed in place or can be preformed and then assembled on site to forman integral impoundment structure. For example, the impoundment can beconstructed by cast forming in place as a monolithic body, extrusion,stacking of preformed or precast pieces, concrete panels joined by agrout (cement, ECC, or other suitable material), inflated form, or thelike. The forms can be built up against a formation or can be standalone structures. Forms can be constructed of any suitable material suchas, but not limited to, steel, wood, fiberglass, polymer, or the like.The forms can be assembled in place or may be oriented using a crane orother suitable mechanism. Alternatively, the constructed permeabilitycontrol infrastructure can be formed of gabions and/or geosyntheticfabrics assembled in layers with compacted fill material. Optionalbinders can be added to enhance compaction of the permeability controlwalls. In yet another detailed aspect, the control infrastructure cancomprise, or consists essentially of, sealant, grout, rebar, syntheticclay, bentonite clay, clay lining, refractory cement, high temperaturegeomembranes, drain pipes, alloy sheets, or combinations thereof.

Impoundment walls can optionally include non-permeable insulation and/orfines collection layers. These permeable layers can be oriented betweenthe permeability control barrier and the permeable body. For example, alayer of hydrocarbonaceous comminuted material can be provided whichallows fluids to enter, cool, and at least partially condense within thelayer. Such permeable layer material can generally have a particle sizesmaller than the permeable body. Further, such hydrocarbonaceousmaterial can remove fines from passing fluids via various attractiveforces. In one embodiment, the construction of impoundment walls andfloors can include multiple compacted layers of indigenous ormanipulated low grade shale with any combination of sand, cement, fiber,plant fiber, nano carbons, crushed glass, reinforcement steel,engineered carbon reinforcement grid, calcium salts, and the like. Inaddition to such composite walls, designs which inhibit long term fluidand gas migration through additional impermeability engineering can beemployed including, but not limited to, liners, geo-membranes, compactedsoils, imported sand, gravel or rock and gravity drainage contours tomove fluids and gases away from impervious layers to egress exits.Impoundment floor and wall construction, can, but need not comprise, astepped up or stepped down slope or bench as the case of mining coursemay dictate following the optimal ore grade mining. In any such steppedup or down applications, floor leveling and containment wallconstruction can typically drain or slope to one side or to a specificcentral gathering area(s) for removal of fluids by gravity drainageassistance.

Optionally, capsule wall and floor construction can include insulationwhich prevents heat transfer outside of the constructed infrastructureor outside of inner capsules or conduits within the primary constructedcapsule containment. Insulation can comprise manufactured materials,cement or various materials other materials which are less thermallyconductive than surrounding masses, i.e. permeable body, formation,adjacent infrastructures, etc. Thermally insulating barriers can also beformed within the permeable body, along impoundment walls, ceilings,and/or floors. One detailed aspect includes the use of biodegradableinsulating materials, e.g. soy insulation and the like. This isconsistent with embodiments wherein the impoundment is a single usesystem such that insulations, pipes, and/or other components can have arelatively low useful life, e.g. less than 1-2 years. This can reduceequipment costs as well as reduce long-term environmental impact.

These structures and methods can be applied at almost any scale. Largerencapsulated volumes and increased numbers of impoundments can readilyproduce hydrocarbon products and performance comparable to or exceedingsmaller constructed infrastructures. As an illustration, singleimpoundments can range in size from tens of meters across to tens ofacres. Optimal impoundment sizes may vary depending on thehydrocarbonaceous material and operating parameters, however it isexpected that suitable areas can range from about one-half to five acresin top plan surface area.

The methods and infrastructures can be used for recovery of hydrocarbonsfrom a variety of hydrocarbonaceous materials. One particular advantageis a wide degree of latitude in controlling particle size, conditions,and composition of the permeable body introduced into the encapsulatedvolume. Non-limiting examples of mined hydrocarbonaceous material whichcan be treated comprise oil shale, tar sands, coal, lignite, bitumen,peat, or combinations thereof. In some cases it can be desirable toprovide a single type of hydro carbonaceous material so that thepermeable body consists essentially of one of the above materials.However, the permeable body can include mixtures of these materials suchthat grade, oil content, hydrogen content, permeability and the like canbe adjusted to achieve a desired result. Further, different hydrocarbonmaterials can be placed in multiple layers or in a mixed fashion such ascombining coal, oil shale, tar sands, biomass, and/or peat.

In one embodiment, hydrocarbon containing material can be classifiedinto various inner capsules within a primary constructed infrastructurefor optimization reasons. For instance, layers and depths of mined oilshale formations may be richer in certain depth pay zones as they aremined. Once blasted, mined, shoveled, and hauled inside of capsule forplacement, richer oil bearing ores can be classified or mixed byrichness for optimal yields, faster recovery, or for optimal averagingwithin each impoundment. Further, providing layers of differingcomposition can have added benefits. For example, a lower layer of tarsands can be oriented below an upper layer of oil shale. Generally, theupper and lower layers can be in direct contact with one anotheralthough this is not required. The upper layer can include heating pipesembedded therein as described in more detail below. The heating pipescan heat the oil shale sufficient to liberate kerogen oil, includingshort-chain liquid hydrocarbons, which can act as a solvent for bitumenremoval from the tar sands. In this manner, the upper layer acts as anin situ solvent source for enhancing bitumen removal from the lowerlayer. Heating pipes within the lower layer are optional such that thelower layer can be free of heating pipes or may include heating pipes,depending on the amount of heat transferred via downward passing liquidsfrom the upper layer and any other heat sources. The ability toselectively control the characteristics and composition of the permeablebody adds a significant amount of freedom in optimizing oil yields andquality.

Furthermore, in many embodiments, the liberated gaseous and liquidproducts act as an in situ produced solvent which supplements kerogenremoval and/or additional hydrocarbon removal from the hydrocarbonaceousmaterial.

In yet another detailed aspect, the permeable body can further comprisean additive or biomass. Additives can include any composition which actsto increase the quality of removed hydrocarbons, e.g. increased API,decreased viscosity, improved flow properties, reduced wetting ofresidual shale, reduction of sulfur, hydrogenation agents, etc.Non-limiting examples of suitable additives can include bitumen,kerogen, propane, natural gas, natural gas condensate, crude oil,refining bottoms, asphaltenes, common solvents, other diluents, andcombinations of these materials. In one specific embodiment, theadditive can include a flow improvement agent and/or a hydrogen donoragent. Some materials can act as both or either agents to improve flowor as a hydrogen donor. Non-limiting examples of such additives caninclude methane, natural gas condensates, common solvent such asacetone, toluene, benzene, etc., and other additives listed above.Additives can act to increase the hydrogen to carbon ratio in anyhydrocarbon products, as well as act as a flow enhancement agent. Forexample, various solvents and other additives can create a physicalmixture which has a reduced viscosity and/or reduced affinity forparticulate solids, rock, and the like. Further, some additives canchemically react with hydrocarbons and/or allow liquid flow of thehydrocarbon products. Any additives used can become part of a finalrecovered product or can be removed and reused or otherwise disposed of.

Similarly, biological hydroxylation of hydrocarbonaceous materials toform synthetic gas or other lighter weight products can be accomplishedusing known additives and approaches. Enzymes or biocatalysts can alsobe used in a similar manner. Further, manmade materials can also be usedas additives such as, but not limited to, tires, polymeric refuse, orother hydrocarbon-containing materials.

Although these methods are broadly applicable, as a general guideline,the permeable body can include particles from about ⅛ inch to about 6feet in largest dimension, and in some cases less than 1 foot and inother cases less than about 6 inches. However, as a practical matter,sizes from about 2 inches to about 2 feet can provide good results withabout 1 foot diameter being useful for oil shale especially. Void spacecan be an important factor in determining optimal particle diameters. Asa general matter, any functional void space can be used; however, about10% to about 50% and in some cases about 30% to about 45% usuallyprovides a good balance of permeability and effective use of availablevolumes. Void volumes can be varied somewhat by varying other parameterssuch as heating conduit placement, additives, and the like. Mechanicalseparation of mined hydrocarbonaceous materials allows creation of finemesh, high permeability particles which enhance thermal dispersion ratesonce placed in capsule within the impoundment. The added permeabilityallows for more reasonable, low temperatures which also help to avoidhigher temperatures which result in greater CO₂ production fromcarbonate decomposition and associated release of trace heavy metals,volatile organics, and other compounds which can create toxic effluentand/or undesirable materials which are monitored and controlled.

Carbon dioxide that is produced during the recovery process can besequestered using one or more approaches. In particular, carbon dioxidecan be converted to a solid or liquid form such that the associatedcarbon is precipitated or otherwise converted to a useful product. Suchsequestering can be optionally accomplished by reacting carbon dioxidewith an aqueous solution to form a precipitation of carbon dioxide witha metal. When referring to carbon dioxide precipitates or precipitatingcarbon dioxide, it is understood that precipitation consumes the carbondioxide such that the carbon dioxide no longer exists as a CO₂structure. As such, the process is generally irreversible and differsfrom general adsorption techniques, which can also be used forsequestering carbon dioxide as further described herein. In oneembodiment, the aqueous solution can be an ionic solution. In anotherembodiment, the aqueous solution can be salt water. The metal can be anymetal that is capable of forming a solid with carbon dioxide includingoxides thereof. In one embodiment, the metal can be calcium, magnesium,including oxides thereof, silicates thereof, and mixtures thereof. Inone embodiment, the metal can be in the form of forsterite, serpentineand/or peridotite. In one embodiment, the exhausted hydrocarbonaceousmaterials can be injected or admixed with the carbon dioxide and saltwater to form carbon dioxide precipitates. Such a process can takeadvantage of metals found in the exhausted hydrocarbonaceous materials.

Additionally, other materials can be added to increase the reactionkinetics to form the carbon dioxide precipitate. For example, theaddition of acids, catalysts, or other organic compounds may increasethe reaction kinetics. Such sequestering can also produce heat duringthe sequestering process. In one embodiment, the heat can be redirectedand applied to the heating step as discussed herein. Such recycling ofheat can further provide a more efficient recovery system.

Additionally, or alternatively, sequestering of carbon dioxide can beachieved by cryogenic precipitation forming liquid carbon dioxide. Thecollected carbon dioxide can be liquefied by lowering the temperature.Such liquid carbon dioxide can then be transferred to a container fordisposal or for reuse. In one embodiment, the liquid carbon dioxide canbe reacted to form polycarbonates, which can provide a stable form fordisposal or potential use in other industries. In another embodiment,the liquid carbon dioxide can be used to further process the exhaustedhydrocarbonaceous materials, as further discussed herein, includingrinsing the hydrocarbonaceous materials during the recovery process.Such treatment can provide additional recovery of hydrocarbons that havenot been removed during the initial recovery process as describedherein.

The sequestered carbon dioxide can be used in other commercialprocesses. In one embodiment, carbon dioxide can be used to isolatepolymers from fluids. For example, carbon dioxide can be used to isolatepolycarbonates from a solvent, e.g. methylene chloride. In anotherembodiment, carbon dioxide can be pumped into depleted permeable bodies.In the case of permeable bodies having a high coal content, once theinitial stores of methane or other products are recovered, CO₂ can bepumped into the impoundment, where it is stored in the coal, which canthen provide the benefit of releasing additional methane. Between threeand thirteen molecules of CO₂ can be absorbed for each molecule ofmethane, making coal an excellent storage location for CO₂.

In one embodiment, storage of carbon dioxide can be performed in deepsaline aquifers or brine-saturated rock formations that occur deepunderground or under the ocean. Specifically, wells deep undergroundconsisting of porous rock, such as limestone or sandstone, saturatedwith saltwater can form an effective trap for injected CO₂.Geologically, over time, some CO₂ can react with rock minerals to formsolid carbonates, further immobilizing the same.

Additionally, a liquid carbon dioxide can be optionally mixed and/oradsorbed by the exhausted hydrocarbonaceous materials. Such materialscan then be disposed in an appropriate manner. When referring to liquidcarbon dioxide, the embodiments herein can also be used withsupercritical carbon dioxide. As such, the discussion and embodimentspresented herein referring to liquid carbon dioxide also can be appliedwith respect to supercritical carbon dioxide.

In another embodiment, sequestering carbon dioxide can be achieved byinjecting exhausted hydrocarbonaceous materials with the carbon dioxide.Such injection can provide adsorption of carbon dioxide. Additionally,such process can be performed with a catalyst or without a catalyst.Other metal and organic additives can be included as discussed herein.In one embodiment, such sequestering can include a metal selected fromthe group consisting of calcium, magnesium, including oxides thereof,silicates thereof, and mixtures thereof.

With respect to carbon dioxide sequestering, a constructed permeabilitycontrol infrastructure can comprise a permeability control impoundmentdefining a substantially encapsulated volume wherein the permeabilitycontrol impoundment is substantially free of undisturbed geologicalformations, a comminuted hydrocarbonaceous material within theencapsulated volume forming a permeable body of hydrocarbonaceousmaterial, and a carbon dioxide collection unit operatively connected tocollect carbon dioxide from the control infrastructure. It is understoodthat the infrastructure can include any of the elements described hereinincluding those elements that have been referred to in the context of aprocess. Additionally, the methods and processes described herein caninclude any elements described herein including those elements that havebeen referred to in the context of a composition or system.

The carbon dioxide can be collected consistent with one or more of theabove approaches using a corresponding carbon dioxide control unit. Inone optional aspect, the carbon dioxide control unit can include avessel for treatment and/or storage of the carbon dioxide. Additionalstorage tanks, pumps and/or vessels can also be used for transporting orstorage of treatment chemicals and by-products. As described herein, thevessel can contain an aqueous solution, a metal, and carbon dioxidewhere the vessel is configured to react the carbon dioxide with theaqueous solution to form a precipitation of carbon dioxide with themetal. In another embodiment, the vessel can contain carbon dioxidewhere the vessel is configured to form liquid carbon dioxide from thecarbon dioxide by cryogenic precipitation. Additionally, the vessel cancontain exhausted hydrocarbonaceous materials that adsorb the liquidcarbon dioxide. In one embodiment, the vessel can contain carbon dioxidewhere the vessel is configured to mix exhausted hydrocarbonaceousmaterials with the carbon dioxide such that the exhaustedhydrocarbonaceous materials adsorb the carbon dioxide.

In one embodiment, computer assisted mining, mine planning, hauling,blasting, assay, loading, transport, placement, and dust controlmeasures can be utilized to fill and optimize the speed of minedmaterial movement into the constructed capsule containment structure. Inone alternative aspect, the impoundments can be formed in excavatedvolumes of a hydrocarbonaceous formation, although other locationsremote from the control infrastructure can also be useful. For example,some hydrocarbonaceous formations have relatively thin hydrocarbon-richlayers, e.g. less than about 300 feet thick. Therefore, vertical miningand drilling tend to not be cost effective. In such cases, horizontalmining can be useful to recover the hydrocarbonaceous materials forformation of the permeable body. Although horizontal mining continues tobe a challenging endeavor, a number of technologies have been developedand continue to be developed which can be useful in connection with theimpoundments. In such cases, at least a portion of the impoundment canbe formed across a horizontal layer, while other portions of theimpoundment can be formed along and/or adjacent non-hydrocarbon bearingformation layers. Other mining approaches such as, but not limited to,room and pillar mining can provide an effective source ofhydrocarbonaceous material with minimal waste and/or reclamation whichcan be transported to an impoundment and treated in accordance with thethese principles.

As mentioned herein, these systems and processes allow for a largedegree of control regarding properties and characteristics of thepermeable body which can be designed and optimized for a giveninstallation. Impoundments, individually and across a plurality ofimpoundments can be readily tailored and classified based on varyingcomposition of materials, intended products and the like. For example,several impoundments can be dedicated to production of heavy crude oil,while others can be configured for production of lighter products and/orsyn gas. Non-limiting example of potential classifications and factorscan include catalyst activity, enzymatic reaction for specific products,aromatic compounds, hydrogen content, microorganism strain or purpose,upgrading process, target final product, pressure (effects productquality and type), temperature, swelling behavior, aquathermalreactions, hydrogen donor agents, heat superdisposition, garbageimpoundment, sewage impoundment, reusable pipes, and others. Typically,a plurality of these factors can be used to configure impoundments in agiven project area for distinct products and purposes.

The comminuted hydrocarbonaceous material can be filled into the controlinfrastructure to form the permeable body in any suitable manner.Typically the comminuted hydrocarbonaceous material can be conveyed intothe control infrastructure by dumping, conveyors or other suitableapproaches. As mentioned previously, the permeable body can have asuitably high void volume. Indiscriminate dumping can result inexcessive compaction and reduction of void volumes. Thus, the permeablebody can be formed by low compaction conveying of the hydrocarbonaceousmaterial into the infrastructure. For example, retracting conveyors canbe used to deliver the material near a top surface of the permeable bodyas it is formed. In this way, the hydrocarbonaceous material can retaina significant void volume between particles without substantial furthercrushing or compaction despite some small degree of compaction whichoften results from lithostatic pressure as the permeable body is formed.

Once a desired permeable body has been formed within the controlinfrastructure, heat can be introduced sufficient to begin removal ofhydrocarbons, e.g. via pyrolysis. A suitable heat source can bethermally associated with the permeable body. Optimal operatingtemperatures within the permeable body can vary depending on thecomposition and desired products. However, as a general guideline,operating temperatures can range from about 200° F. to about 750° F.Temperature variations throughout the encapsulated volume can vary andmay reach as high as 900° F. or more in some areas. In one embodiment,the operating temperature can be a relatively lower temperature tofacilitate production of liquid product such as from about 200° F. toabout 650° F. This heating step can be a roasting operation whichresults in beneficiation of the crushed ore of the permeable body.Further, one embodiment comprises controlling the temperature, pressureand other variables sufficient to produce predominantly, and in somecases substantially only, liquid product. Generally, products caninclude both liquid and gaseous products, while liquid products canrequire fewer processing steps such as scrubbers etc. The relativelyhigh permeability of the permeable body allows for production of liquidhydrocarbon products and minimization of gaseous products, depending tosome extent on the particular starting materials and operatingconditions. In one embodiment, the recovery of hydrocarbon products canoccur substantially in the absence of cracking within the permeablebody.

In one aspect, heat can be transferred to the permeable body viaconvection. Heated gases can be injected into the control infrastructuresuch that the permeable body is primarily heated via convection as theheated gases pass throughout the permeable body. Heated gases can beproduced by combustion of natural gas, hydrocarbon product, or any othersuitable source. Non-limiting examples of suitable heat transfer fluidscan include hot air, hot exhaust gases, steam, hydrocarbon vapors and/orhot liquids. The heated gases can be imported from external sources orrecovered from the process.

Alternatively, or in combination with convective heating, a highlyconfigurable approach can include embedding a plurality of conduitswithin the permeable body. The conduits can be configured for use asheating pipes, cooling pipes, heat transfer pipes, drainage pipes, orgas pipes. Further, the conduits can be dedicated to a single functionor may serve multiple functions during operation of the infrastructure,i.e. heat transfer and drainage. The conduits can be formed of anysuitable material, depending on the intended function. Non-limitingexamples of suitable materials can include clay pipes, refractory cementpipes, refractory ECC pipes, poured in place pipes, metal pipes such ascast iron, stainless steel etc., polymer such as PVC, and the like. Inone specific embodiment, all or at least a portion of the embeddedconduits can comprise a degradable material. For example, non-galvanized6″ cast iron pipes can be effectively used for single use embodimentsand perform well over the useful life of the impoundment, typically lessthan about 2 years. Further, different portions of the plurality ofconduits can be formed of different materials. Poured in place pipes canbe especially useful for very large encapsulation volumes where pipediameters exceed several feet. Such pipes can be formed using flexiblewraps which retain a viscous fluid in an annular shape. For example, PVCpipes can be used as a portion of a form along with flexible wraps,where concrete or other viscous fluid is pumped into an annular spacebetween the PVC and flexible wrap. Depending on the intended function,perforations or other apertures can be made in the conduits to allowfluids to flow between the conduits and the permeable body. Typicaloperating temperatures exceed the melting point of conventional polymerand resin pipes. In some embodiments, the conduits can be placed andoriented such that the conduits intentionally melt or otherwise degradeduring operation of the infrastructure.

The plurality of conduits can be readily oriented in any configuration,whether substantially horizontal, vertical, slanted, branched, or thelike. At least a portion of the conduits can be oriented alongpredetermined pathways prior to embedding the conduits within thepermeable body. The predetermined pathways can be designed to improveheat transfer, gas-liquid-solid contacting, maximize fluid delivery orremoval from specific regions within the encapsulated volume, or thelike. Further, at least a portion the conduits can be dedicated toheating of the permeable body. These heating conduits can be selectivelyperforated to allow heated gases or other fluids to convectively heatand mix throughout the permeable body. The perforations can be locatedand sized to optimize even and/or controlled heating throughout thepermeable body. Alternatively, the heating conduits can form a closedloop such that heating gases or fluids are segregated from the permeablebody. Thus, a “closed loop” does not necessarily require recirculation,rather isolation of heating fluid from the permeable body. In thismanner, heating can be accomplished primarily or substantially onlythrough thermal conduction across the conduit walls from the heatingfluids into the permeable body. Heating in a closed loop allows forprevention of mass transfer between the heating fluid and permeable bodyand can reduce formation and/or extraction of gaseous hydrocarbonproducts.

During the heating or roasting of the permeable body, localized areas ofheat which exceed parent rock decomposition temperatures, often aboveabout 900° F., can reduce yields and form carbon dioxide and undesirablecontaminating compounds which can lead to leachates containing heavymetals, soluble organics and the like. The heating conduits can allowfor substantial elimination of such localized hot spots whilemaintaining a vast majority of the permeable body within a desiredtemperature range. The degree of uniformity in temperature can be abalance of cost (e.g. for additional heating conduits) versus yields.However, at least about 85% of the permeable body can readily bemaintained within about 5-10% of a target temperature range withsubstantially no hot spots, i.e. exceeding the decomposition temperatureof the hydrocarbonaceous materials such as about 800° F. and in manycases about 900° F. Thus, operated as described herein, the systems canallow for recovery of hydrocarbons while eliminating or substantiallyavoiding production of undesirable leachates. Although products can varyconsiderably depending on the starting materials, high quality liquidand gaseous products are possible. In accordance with one embodiment, acrushed oil shale material can produce a liquid product having an APIfrom about 30 to about 45, with about 33 to about 38 being currentlytypical, directly from the oil shale without additional treatment.Interestingly, practice of these processes has led to an understandingthat pressure appears to be a much less influential factor on thequality of recovered hydrocarbons than temperature and heating times.Although heating times can vary considerably, depending on void space,permeable body composition, quality, etc., as a general guideline timescan range from a few days (i.e. 3-4 days) up to about one year. In onespecific example, heating times can range from about 2 weeks to about 4months. Under-heating oil shale at short residence times, i.e. minutesto several hours, can lead to formation of leachable and/or somewhatvolatile hydrocarbons. Accordingly, these systems and methods allow forextended residence times at moderate temperatures such that organicspresent in oil shale can be volatilized and/or carbonized, leavinginsubstantial leachable organics. In addition, the underlying shale isnot generally decomposed or altered which reduces soluble saltformation.

Further, conduits can be oriented among a plurality of impoundmentsand/or control infrastructures to transfer fluids and/or heat betweenthe structures. The conduits can be welded to one another usingconventional welding or the like. Further, the conduits can includejunctions which allow for rotation and or small amounts of movementduring expansion and subsidence of material in the permeable body.Additionally, the conduits can include a support system which acts tosupport the assembly of conduits prior to and during filling of theencapsulated volume, as well as during operation. For example, duringheating flows of fluids, heating and the like can cause expansion(fracturing or popcorn effect) or subsidence sufficient to createpotentially damaging stress and strain on the conduits and associatedjunctions. A truss support system or other similar anchoring members canbe useful in reducing damage to the conduits. The anchoring members caninclude cement blocks, 1-beams, rebar, columns, etc. which can beassociated with walls of the impoundment, including side walls, floorsand ceilings.

Alternatively, the conduits can be completely constructed and assembledprior to introduction of any mined materials into the encapsulatedvolume. Care and planning can be considered in designing thepredetermined pathways of the conduits and method of filling the volumein order to prevent damage to the conduits during the filling process asthe conduits are buried. Thus, as a general rule, the conduits areoriented ab initio, or prior to embedding in the permeable body suchthat they are non-drilled. As a result, construction of the conduits andplacement thereof can be performed without extensive core drillingand/or complicated machinery associated with well-bore or horizontaldrilling. Rather, horizontal or any other orientation of conduit can bereadily achieved by assembling the desired predetermined pathways priorto, or contemporaneous with, filling the infrastructure with the minedhydrocarbonaceous material. The non-drilled, hand/crane-placed conduitsoriented in various geometric patterns can be laid with valve controlledconnecting points which yield precise and closely monitored heatingwithin the capsule impoundment. The ability to place and layer conduitsincluding connecting, bypass and flow valves, and direct injection andexit points, allow for precision temperature and heating rates,precision pressure and pressurization rates, and precision fluid and gasingress, egress and composition admixtures. For example, when abacteria, enzyme, or other biological material is used, optimaltemperatures can be readily maintained throughout the permeable body toincrease performance, reaction, and reliability of such biomaterials.

The conduits will generally pass through walls of the constructedinfrastructure at various points. Due to temperature differences andtolerances, it can be beneficial to include an insulating material atthe interface between the wall and the conduits. The dimensions of thisinterface can be minimized while also allowing space for thermalexpansion differences during startup, steady-state operation,fluctuating operating conditions, and shutdown of the infrastructure.The interface can also involve insulating materials and sealant deviceswhich prevent uncontrolled egress of hydrocarbons or other materialsfrom the control infrastructure. Non-limiting examples of suitablematerials can include high temperature gaskets, metal alloys, ceramics,clay or mineral liners, composites or other materials which havingmelting points above typical operating temperatures and act as acontinuation of the permeability control provided by walls of thecontrol infrastructure.

Further, walls of the constructed infrastructure can be configured tominimize heat loss. In one aspect, the walls can be constructed having asubstantially uniform thickness which is optimized to provide sufficientmechanical strength while also minimizing the volume of wall materialthrough which the conduits pass. Specifically, excessively thick wallscan reduce the amount of heat which is transferred into the permeablebody by absorbing the same through conduction. Conversely, the walls canalso act as a thermal barrier to somewhat insulate the permeable bodyand retain heat therein during operation.

In one embodiment, fluid and gas compounds within the permeable body canbe altered for desired extractive products using, as an example, inducedpressure through gases or piled lithostatic pressure from piled rubble.Thus, some degree of upgrading and/or modification can be accomplishedsimultaneous with the recovery process. Further, certain hydrocarbonaceous materials can require treatment using specific diluents orother materials. For example, treatment of tar sands can be readilyaccomplished by steam injection or solvent injection to facilitateseparation of bitumen from sand particles according to well knownmechanisms.

With the above description in mind, FIG. 1 depicts a side view of oneembodiment showing an engineered capsule containment and extractionimpoundment 100 where existing grade 108 is used primarily as supportfor the impermeable floor layer 112. Exterior capsule impoundment sidewalls 102 provide containment and can, but need not be, subdivided byinterior walls 104. Subdividing can create separate containment capsules122 within a greater capsule containment of the impoundment 100 whichcan be any geometry, size or subdivision. Further subdivisions can behorizontally or vertically stacked. By creating separate containmentcapsules 122 or chambers, classification of lower grade materials,varied gases, varied liquids, varied process stages, varied enzymes ormicrobiology types, or other desired and staged processes can be readilyaccommodated. Sectioned capsules constructed as silos within largerconstructed capsules can also be designed to provide staged andsequenced processing, temperatures, gas and fluid compositions andthermal transfers. Such sectioned capsules can provide additionalenvironmental monitoring and can be built of lined and engineeredtailings berms similar to the primary exterior walls. In one embodiment,sections within the impoundment 100 can be used to place materials inisolation, in the absence of external heat, or with the intent oflimited or controlled combustion or solvent application. Lower contenthydrocarbon bearing material can be useful as a combustion material oras fill or a berm wall building material. Material which does not meet avarious cut-off grade thresholds can also be sequestered withoutalteration in an impoundment dedicated for such purpose. In suchembodiments, such areas may be completely isolated or bypassed by heat,solvents, gases, liquids, or the like. Optional monitoring devicesand/or equipment can be permanently or temporarily installed within theimpoundment or outside perimeters of the impoundments in order to verifycontainment of the sequestered material.

Walls 102 and 104 as well as cap 116 and impermeable layer 112 can beengineered and reinforced by gabions 146 and or geogrid 148 layered infill compaction. Alternatively, these walls 102, 104, 116 and 112 whichcomprise the permeability control impoundment and collectively definethe encapsulated volume can be formed of any other suitable material aspreviously described. In this embodiment, the impoundment 100 includesside walls 102 and 104 which are self-supporting. In one embodiment,tailings berms, walls, and floors can be compacted and engineered forstructure as well as permeability. The use of compacted geogrids andother deadman structures for support of berms and embankments can beincluded prior to or incorporated with permeability control layers whichmay include sand, clay, bentonite clay, gravel, cement, grout,reinforced cement, refractory cements, insulations, geo-membranes,drainpipes, temperature resistant insulations of penetrating heatedpipes, etc.

In one alternative embodiment, the permeability control impoundment caninclude side walls which are compacted earth and/or undisturbedgeological formations while the cap and floors are impermeable.Specifically, in such embodiments an impermeable cap can be used toprevent uncontrolled escape of volatiles and gases from the impoundmentsuch that appropriate gas collection outlets can be used. Similarly, animpermeable floor can be used to contain and direct collected liquids toa suitable outlet such the drain system 133 to remove liquid productsfrom lower regions of the impoundment. Although impermeable side wallscan be desirable in some embodiments, such are not always required. Insome cases, side walls can be exposed undisturbed earth or compactedfill or earth, or other permeable material. Having permeable side wallsmay allow some small egress of gases and/or liquids from theimpoundment.

Although not shown, above, below, around and adjacent to constructedcapsule containment vessels environmental hydrology measures can beengineered to redirect surface water away from the capsule walls,floors, caps, etc. during operation. Further, gravity assisted drainagepipes and mechanisms can be utilized to aggregate and channel fluids,liquids or solvents within the encapsulated volume to central gathering,pumping, condensing, heating, staging and discharge pipes, silos, tanks,and/or wells as needed. In a similar manner, steam and/or water which isintentionally introduce, e.g. for tar sands bitumen treatment, can berecycled.

Once wall structures 102 and 104 have been constructed above aconstructed and impermeable floor layer 112 which commences from groundsurface 106, the mined rubble 120 (which may be crushed or classifiedaccording to size or hydrocarbon richness), can be placed in layers upon(or next to) placed tubular heating pipes 118, fluid drainage pipes 124,and, or gas gathering or injection pipes 126. These pipes can beoriented and designed in any optimal flow pattern, angle, length, size,volume, intersection, grid, wall sizing, alloy construction, perforationdesign, injection rate, and extraction rate. In some cases, pipes suchas those used for heat transfer can be connected to, recycled through orderive heat from heat source 134. Alternatively, or in combination with,recovered gases can be condensed by a condenser 140. Heat recovered bythe condenser can be optionally used to supplement heating of thepermeable body or for other process needs.

Heat source 134 can derive, amplify, gather, create, combine, separate,transmit or include heat derived from any suitable heat sourceincluding, but not limited to, fuel cells (e.g. solid oxide fuel cells,molten carbonate fuel cells and the like), solar sources, wind sources,hydrocarbon liquid or gas combustion heaters, geothermal heat sources,nuclear power plant, coal fired power plant, radio frequency generatedheat, wave energy, flameless combustors, natural distributed combustors,or any combination thereof. In some cases, electrical resistive heatersor other heaters can be used, although fuel cells and combustion-basedheaters are particularly effective. In some locations, geothermal watercan be circulated to the surface in adequate amounts to heat thepermeable body and directed into the infrastructure.

In another embodiment, electrically conductive material can bedistributed throughout the permeable body and an electric current can bepassed through the conductive material sufficient to generate heat. Theelectrically conductive material can include, but is not limited to,metal pieces or beads, conductive cement, metal coated particles,metal-ceramic composites, conductive semi-metal carbides, calcinedpetroleum coke, laid wire, combinations of these materials, and thelike. The electrically conductive material can be premixed havingvarious mesh sizes or the materials can be introduced into the permeablebody subsequent to formation of the permeable body.

Liquids or gases can transfer heat from heat source 134, or in anotherembodiment, in the cases of hydrocarbon liquid or gas combustion, radiofrequency generators (microwaves), or fuel cells all can, but need not,actually generate heat inside of capsule impoundment area 114 or 122. Inone embodiment, heating of the permeable body can be accomplished byconvective heating from hydrocarbon combustion. Of particular interestis hydrocarbon combustion performed under stoichiometric conditions offuel to oxygen. Stoichiometric conditions can allow for significantlyincreased heat gas temperatures. Stoichiometric combustion can employbut does not generally require a pure oxygen source which can beprovided by known technologies including, but not limited to, oxygenconcentrators, membranes, electrolysis, and the like. In someembodiments oxygen can be provided from air with stoichiometric amountsof oxygen and hydrogen. Combustion off gas can be directed to anultra-high temperature heat exchanger, e.g. a ceramic or other suitablematerial having an operating temperature above about 2500° F. Airobtained from ambient or recycled from other processes can be heated viathe ultra high temperature heat exchanger and then sent to theimpoundment for heating of the permeable body. The combustion off gasescan then be sequestered without the need for further separation, i.e.because the off gas is predominantly carbon dioxide and water.

In order to minimize heat losses, distances can be minimized between thecombustion chamber, heat exchanger, and impoundments. Therefore, in onespecific detailed embodiment portable combustors can be attached toindividual heating conduits or smaller sections of conduits. Portablecombustors or burners can individually provide from about 100,000 Btu toabout 1,000,000 Btu with about 600,000 Btu per pipe generally beingsufficient.

Alternatively, in-capsule combustion can be initiated inside of isolatedcapsules within a primary constructed capsule containment structure.This process partially combusts hydrocarbonaceous material to provideheat and intrinsic pyrolysis. Unwanted air emissions 144 can be capturedand sequestered in a formation 108 once derived from capsule containment114, 122 or from heat source 134 and delivered by a drilled well bore142. Heat source 134 can also create electricity and transmit, transformor power via electrical transmission lines 150. The liquids or gasesextracted from capsule impoundment treatment area 114 or 122 can bestored in a nearby holding tank 136 or within a capsule containment 114or 122. For example, the impermeable floor layer 112 can include asloped area 110 which directs liquids towards drain system 133 whereliquids are directed to the holding tank.

As rubble material 120 is placed with piping 118, 124, 126, and 128,various measurement devices or sensors 130 are envisioned to monitortemperature, pressure, fluids, gases, compositions, heating rates,density, and all other process attributes during the extractive processwithin, around, or underneath the engineered capsule containmentimpoundment 100. Such monitoring devices and sensors 130 can bedistributed anywhere within, around, part of, connected to, or on top ofplaced piping 118, 124, 126, and 128 or, on top of, covered by, orburied within rubble material 120 or impermeable barrier zone 112.

As placed rubble material 120 fills the capsule treatment area 114 or122, 120 becomes the ceiling support for engineered impermeable capbarrier zone 138, and wall barrier construction 170, which may includeany combination of impermeability and engineered fluid and gas barrieror constructed capsule construction comprising those which may make up112 including, but not limited to clay 162, compacted fill or importmaterial 164, cement or refractory cement containing material 166, geosynthetic membrane, liner or insulation 168. Above 138, fill materialwhich can be oriented as ceiling cap 116 is placed to create lithostaticpressure upon the capsule treatment areas 114 or 122. Covering thepermeable body with compacted fill sufficient to create an increasedlithostatic pressure within the permeable body can be useful in furtherincreasing hydrocarbon product quality. A compacted fill ceiling cansubstantially cover the permeable body, while the permeable body inreturn can substantially support the compacted fill ceiling. Thecompacted fill ceiling can further be sufficiently impermeable toremoved hydrocarbon or an additional layer of permeability controlmaterial can be added in a similar manner as side and/or floor walls.Additional pressure can be introduced into extraction capsule treatmentarea 114 or 122 by increasing any gas or fluid once extracted, treatedor recycled, as the case may be, via any of piping 118, 124, 126, or128. All relative measurements, optimization rates, injection rates,extraction rates, temperatures, heating rates, flow rates, pressurerates, capacity indicators, chemical compositions, or other datarelative to the process of heating, extraction, stabilization,sequestration, impoundment, upgrading, refining or structure analysiswithin the capsule impoundment 100 are envisioned through connection toa computing device 132 which operates computer software for themanagement, calculation and optimization of the entire process. Further,core drilling, geological reserve analysis and assay modeling of aformation prior to blasting, mining and hauling (or at any time before,after or during such tasks) can serve as data input feeds into computercontrolled mechanisms that operate software to identify optimalplacements, dimensions, volumes and designs calibrated and crossreferenced to desired production rate, pressure, temperature, heat inputrates, gas weight percentages, gas injection compositions, heatcapacity, permeability, porosity, chemical and mineral composition,compaction, density. Such analysis and determinations may include otherfactors like weather data factors such as temperature and air moisturecontent impacting the overall performance of the constructedinfrastructure. Other data such as ore moisture content, hydrocarbonrichness, weight, mesh size, and mineral and geological composition canbe utilized as inputs including time value of money data sets yieldingproject cash flows, debt service, and internal rates of return.

FIG. 2A shows a collection of impoundments including an uncovered oruncapped capsule impoundment 100, containing sectioned capsuleimpoundments 122 inside of a mining quarry 200 with various elevationsof bench mining. FIG. 2B illustrates a single impoundment 122 withoutassociated conduits and other aspects merely for clarity. Thisimpoundment can be similar to that illustrated in FIG. 1 or any otherconfiguration. In some embodiments, it is envisioned that mining rubblecan be transferred down chutes 230 or via conveyors 232 to the quarrycapsule impoundments 100 and 122 without any need of mining haul trucks.

FIG. 3 shows the engineered permeability barriers 112 below capsuleimpoundment 100 resting on existing grade 106 of formation 108 with capcovering material or fill 302 on the sides and top of capsuleimpoundment 100 to ultimately (following the process) cover and reclaima new earth surface 300. Indigenous plants which may have beentemporarily moved from the area may be replanted such as trees 306. Theconstructed infrastructures can generally be single use structures whichcan be readily and securely shut down with minimal additionalremediation. This can dramatically reduce costs associated with movinglarge volumes of spent materials. However, in some circumstances theconstructed infrastructures can be excavated and reused. Some equipmentsuch as radio frequency (RF) mechanisms, tubulars, devices, and emittersmay be recovered from within the constructed impoundment upon completionof hydrocarbon recovery.

FIG. 4 shows computer means 130 controlling various property inputs andoutputs of conduits 118, 126, or 128 connected to heat source 134 duringthe process among the subdivided impoundments 122 within a collectiveimpoundment 100 to control heating of the permeable body. Similarly,liquid and vapor collected from the impoundments can be monitored andcollected in tank 136 and condenser 140, respectively. Condensed liquidsfrom the condenser can be collected in tank 141, while non-condensablevapor collected at unit 143. As described previously, the liquid andvapor products can be combined or more often left as separate productsdepending on condensability, target product, and the like. A portion ofthe vapor product can be optionally condensed and combined with theliquid products in tank 136. However, much of the vapor product will beC4 and lighter gases which can be burned, sold, or used within theprocess. For example, hydrogen gas may be recovered using conventionalgas separation and used to hydrotreat the liquid products according toconventional upgrading methods, e.g. catalytic, etc. or thenon-condensable gaseous product can be burned to produce heat for use inheating the permeable body, heating an adjacent or nearby impoundment,heating service or personnel areas, or satisfying other process heatrequirements. The constructed infrastructure can include thermocouples,pressure meters, flow meters, fluid dispersion sensors, richness sensorsand any other conventional process control devices distributedthroughout the constructed infrastructure. These devices can be eachoperatively associated with a computer such that heating rates, productflow rates, and pressures can be monitored or altered during heating ofthe permeable body. Optionally, in-place agitation can be performedusing, for example, ultrasonic generators which are associated with thepermeable body. Such agitation can facilitate separation and pyrolysisof hydrocarbons from the underlying solid materials with which they areassociated. Further, sufficient agitation can reduce clogging andagglomeration throughout the permeable body and the conduits.

FIG. 5 shows how any of the conduits can be used to transfer heat in anyform of gas, liquid or heat via transfer means 510 from any sectionedcapsule impoundment to another. Then, cooled fluid can be conveyed viaheat transfer means 512 to the heat originating capsule 500, or heatoriginating source 134 to pick up more heat from capsule 500 to be againrecirculated to a destination capsule 522. Thus, various conduits can beused to transfer heat from one impoundment to another in order torecycle heat and manage energy usage to minimize energy losses.

In yet another aspect, a hydrogen donor agent can be introduced into thepermeable body during the step of heating. The hydrogen donor agent canbe any composition which is capable of hydrogenation of the hydrocarbonsand can optionally be a reducing agent. Non-limiting examples ofsuitable hydrogen donor agents can include synthesis gas, propane,methane, hydrogen, natural gas, natural gas condensate, industrialsolvents such as acetones, toluenes, benzenes, xylenes, cumenes,cyclopentanes, cyclohexanes, lower alkenes (C4-C10), terpenes,substituted compounds of these solvents, etc., and the like. Further,the recovered hydrocarbons can be subjected to hydrotreating eitherwithin the permeable body or subsequent to collection. Advantageously,hydrogen recovered from the gas products can be reintroduced into theliquid product for upgrading. Regardless, hydrotreating orhydrodesulfurization can be very useful in reducing nitrogen and sulfurcontent in final hydrocarbon products. Optionally, catalysts can beintroduced to facilitate such reactions. In addition, introduction oflight hydrocarbons into the permeable body can result in reformingreactions which reduce the molecular weight, while increasing thehydrogen to carbon ratio. This is particularly advantageous due at leastin part to high permeability of the permeable body, e.g. often around30%-40% void volume although void volume can generally vary from about10% to about 50% void volume. Light hydrocarbons which can be injectedcan be any which provide reforming to recovered hydrocarbons.Non-limiting examples of suitable light hydrocarbons include naturalgas, natural gas condensates, industrial solvents, hydrogen donoragents, and other hydrocarbons having ten or fewer carbons, and oftenfive or fewer carbons. Currently, natural gas is an effective,convenient, and plentiful light hydrocarbon. As mentioned previously,various solvents or other additives can also be added to aid inextraction of hydrocarbon products from the oil shale and can often alsoincrease fluidity.

The light hydrocarbon can be introduced into the permeable body byconveying the same through a delivery conduit having an open end influid communication with a lower portion of the permeable body such thatthe light hydrocarbons (which are a gas under normal operatingconditions) permeate up through the permeable body. Alternatively, thissame approach can be applied to recovered hydrocarbons which are firstdelivered to an empty impoundment. In this way, the impoundment can actas a holding tank for direct products from a nearby impoundment and as areformer or upgrader. In this embodiment, the impoundment can be atleast partially filled with a liquid product where the gaseous lighthydrocarbon is passed through and allowed to contact the liquidhydrocarbon products at temperatures and conditions sufficient toachieve reforming in accordance with well known processes. Optionalreforming catalysts which include metals such as Pd, Ni or othersuitable catalytically active metals can also be included in the liquidproduct within the impoundment. The addition of catalysts can serve tolower and/or adjust reforming temperature and/or pressure for particularliquid products. Further, the impoundments can be readily formed atalmost any depth. Thus, optimal reforming pressures (or recoverypressures when using impoundment depth as pressure control measure forrecovery from a permeable body) can be designed based on hydrostaticpressure due to the amount of liquid in the impoundment and the heightof the impoundment, i.e. P=ρgh. In addition, the pressure can varyconsiderably over the height of the impoundment sufficient to providemultiple reforming zones and tailorable pressures. Generally, pressureswithin the permeable body can be sufficient to achieve substantiallyonly liquid extraction, although some minor volumes of vapor may beproduced depending on the particular composition of the permeable body.As a general guideline, pressures can range from about 5 atm to about 50atm, although pressures from about 6 atm to about 20 atm can beparticularly useful. However, any pressure greater than aboutatmospheric can be used.

In one embodiment, extracted crude has fines precipitated out within thesubdivided capsules. Extracted fluids and gases can be treated for theremoval of fines and dust particles. Separation of fines from shale oilcan be accomplished by techniques such as, but not limited to, hot gasfiltering, precipitation, and heavy oil recycling.

Hydrocarbon products recovered from the permeable body can be furtherprocessed (e.g. refined) or used as produced. Any condensable gaseousproducts can be condensed by cooling and collection, whilenon-condensable gases can be collected, burned as fuel, reinjected, orotherwise utilized or disposed of. Optionally, mobile equipment can beused to collect gases. These units can be readily oriented proximate tothe control infrastructure and the gaseous product directed thereto viasuitable conduits from an upper region of the control infrastructure.

In yet another alternative embodiment, heat within the permeable bodycan be recovered subsequent to primary recovery of hydrocarbon materialstherefrom. For example, a large amount of heat is retained in thepermeable body. In one optional embodiment, the permeable body can beflooded with a heat transfer fluid such as water to form a heated fluid,e.g. heated water and/or steam. At the same time, this process canfacilitate removal of some residual hydrocarbon products via a physicalrinsing of the spent shale solids. In some cases, the introduction ofwater and presence of steam can result in water gas shift reactions andformation of synthesis gas. Steam recovered from this process can beused to drive a generator, directed to another nearby infrastructure, orotherwise used. Hydrocarbons and/or synthesis gas can be separated fromthe steam or heated fluid by conventional methods.

Although the methods and infrastructure allow for improved permeabilityand control of operating conditions, significant quantities ofunrecovered hydrocarbons, precious metals, minerals, sodium bicarbonateor other commercially valuable materials often remain in the permeablebody. Therefore, a selective solvent can be injected or introduced intothe permeable body. Typically, this can be done subsequent to collectingthe hydrocarbons, although certain selective solvents can bebeneficially used prior to heating and/or collection. This can be doneusing one or more of the existing conduits or by direct injection andpercolation through the permeable body. The selective solvent orleachate can be chosen as a solvent for one or more target materials,e.g. minerals, precious metal, heavy metals, hydrocarbons, or sodiumbicarbonate. In one specific embodiment, steam or carbon dioxide can beused as a rinse of the permeable body to dislodge at least a portion ofany remaining hydrocarbons. This can be beneficial not only in removingpotentially valuable secondary products, but also in cleaning remainingspent materials of trace heavy metal or inorganics to below detectablelevels in order to comply with regulatory standards or to preventinadvertent leaching of materials at a future date.

More particularly, various recovery steps can be used either before orafter heating of the permeable body to recover heavy metals, preciousmetals, trace metals or other materials which either have economic valueor may cause undesirable problems during heating of the permeable body.Typically, such recovery of materials can be performed prior to heattreatment of the permeable body. Recovery steps can include, but are inno way limited to, solution mining, leaching, solvent recovery,precipitation, acids (e.g. hydrochloric, acidic halides, etc.),flotation, ionic resin exchange, electroplating, or the like. Forexample, heavy metals, bauxite or aluminum, and mercury can be removedby flooding the permeable body with an appropriate solvent andrecirculating the resulting leachate through appropriately designed ionexchange resins (e.g. beads, membranes, etc.).

Similarly, bioextraction, bioleaching, biorecovery, or bioremediation ofhydrocarbon material, spent materials, or precious metals can beperformed to further improve remediation, extract valuable metals, andrestoration of spent material to environmentally acceptable standards.In such bioextraction scenarios, conduits can be used to injectcatalyzing gases as a precursor which helps to encourage bioreaction andgrowth. Such microorganisms and enzymes can biochemically oxidize theore body or material or cellulosic or other biomass material prior to anore solvent extraction via bio-oxidation. For example, a perforated pipeor other mechanism can be used to inject a light hydrocarbon (e.g.methane, ethane, propane or butane) into the permeable body sufficientto stimulate growth and action of native bacteria. Bacteria can benative or introduced and may grow under aerobic or anaerobic conditions.Such bacteria can release metals from the permeable body which can thenbe recovered via flushing with a suitable solvent or other suitablerecovery methods. The recovered metals can then be precipitated outusing conventional methods.

Synthesis gas can also be recovered from the permeable body during thestep of heating. Various stages of gas production can be manipulatedthrough processes which raise or lower operating temperatures within theencapsulated volume and adjust other inputs into the impoundment toproduce synthetic gases which can include but are not limited to, carbonmonoxide, hydrogen, hydrogen sulfide, hydrocarbons, ammonia, water,nitrogen or various combinations thereof. In one embodiment, temperatureand pressure can be controlled within the permeable body to lower CO₂emissions as synthetic gases are extracted.

Hydrocarbon product recovered from the constructed infrastructures canmost often be further processed, e.g. by upgrading, refining, etc.Sulfur from related upgrading and refining processing can be isolated invarious constructed sulfur capsules within the greater structuredimpoundment capsule. Constructed sulfur capsules can be spentconstructed infrastructures or dedicated for the purpose of storage andisolation after desulfurization.

Similarly, spent hydrocarbonaceous material remaining in the constructedinfrastructure can be utilized in the production of cement and aggregateproducts for use in construction or stabilization of the infrastructureitself or in the formation of offsite constructed infrastructures. Suchcement products made with the spent shale may include, but are notlimited to, mixtures with Portland cement, calcium salt, volcanic ash,perlite, synthetic nano carbons, sand, fiber glass, crushed glass,asphalt, tar, binding resins, cellulosic plant fibers, and the like.

In still another embodiment, injection, monitoring and productionconduits or extraction egresses can be incorporated into any pattern orplacement within the constructed infrastructure. Monitoring wells andconstructed geo membrane layers beneath or outside of the constructedcapsule containment can be employed to monitor unwanted fluid andmoisture migration outside of containment boundaries and the constructedinfrastructure.

Although a filled and prepared constructed infrastructure can often beimmediately heated to recover hydrocarbons, this is not required. Forexample, a constructed infrastructure which is built and filled withmined hydrocarbonaceous material can be left in place as a provenreserve. Such structures are less susceptible to explosion or damage dueto terrorist activity and can also provide strategic reserves ofunprocessed petroleum products, with classified and known properties sothat economic valuations can be increased and more predictable. Longterm petroleum storage often faces quality deterioration issues overtime. Thus, these approaches can optionally be used for long termquality insurance and storage with reduced concerns regarding breakdownand degradation of hydrocarbon products.

In still another aspect, the high quality liquid product can be blendedwith more viscous lower quality (e.g. lower API) hydrocarbon products.For example, kerogen oil produced from the impoundments can be blendedwith bitumen to form a blended oil. The bitumen is typically nottransportable through an extended pipeline under conventional andaccepted pipeline standards and can have a viscosity substantially aboveand an API substantially below that of the kerogen oil. By blending thekerogen oil and bitumen, the blended oil can be rendered transportablewithout the use of additional diluents or other viscosity or APImodifiers. As a result, the blended oil can be pumped through a pipelinewithout requiring additional treatments to remove a diluent or returningsuch diluents via a secondary pipeline. Conventionally, bitumen iscombined with a diluent such as natural gas condensate or other lowmolecular weight liquids, to allow pumping to a remote location. Thediluent is removed and returned via a second pipeline back to thebitumen source. These approaches allow for elimination of returningdiluent and simultaneous upgrading of the bitumen.

Difficult problems can thus be solved related to the extraction ofhydrocarbon liquids and gases from surface or underground minedhydrocarbon bearing deposits such as oil shale, tar sands, lignite, andcoal, and from harvested biomass. Among other things, these methods andsystems help reduce cost, increase volume output, lower air emissions,limit water consumption, prevent underground aquifer contamination,reclaim surface disturbances, reduce material handling costs, removedirty fine particulates, and improve composition of recoveredhydrocarbon liquid or gas. Water contamination issues can also beaddressed with a safer, more predictable, engineered, observable,repairable, adaptable and preventable water protection structure.

Although the described methods and systems are mining-dependent, theyare not limited or encumbered to conventional aboveground (ex-situ)retorting processes. This approach improves upon the benefits of surfaceretorts including better process control of temperature, pressure,injection rates, fluid and gas compositions, product quality and betterpermeability due to processing and heating mined rubble. Theseadvantages are available while still addressing the volume, handling,and scalability issues most fabricated surface retorts cannot provide.

Other improvements which can be realized are related to environmentalprotection. Conventional surface retorts have had the problem of spentshale after it has been mined and has passed through a surface retort.Spent shale which has been thermally altered requires special handlingto reclaim and isolate from surface drainage basins and undergroundaquifers. These methods and systems can address reclamation andretorting in a uniquely combined approach. In regards to air emissionswhich are also a major problem typical of prior surface retort methods,this approach, because of its enormous volume capacity and highpermeability, can accommodate longer heating residence times andtherefore lower temperatures. One benefit of lower temperatures in theextraction process is that carbon dioxide production from decompositionof carbonates in the oil shale ore can be substantially limited therebydramatically reducing CO₂ emissions and atmospheric pollutants.

It is to be understood that the above-referenced arrangements areillustrative of the application for the principles of the presentinvention. Thus, while the present invention has been described above inconnection with the exemplary embodiments, it will be apparent to thoseof ordinary skill in the art that numerous modifications and alternativearrangements can be made without departing from the principles andconcepts of the invention as set forth in the claims.

1. A method of sequestering carbon dioxide emissions during recovery ofhydrocarbons from hydrocarbonaceous materials comprising: a) forming aconstructed permeability control infrastructure which defines asubstantially encapsulated volume, said infrastructure comprising clay,bentonite clay, bentonite amended soil, compacted fill, refractorycement, cement, synthetic geogrids, fiberglass, rebar, nanocarbonfullerene additives, filled geotextile bags, polymeric resins, oilresistant PVC liners, engineered cementitious composites (ECC), fiberreinforced composites, geosynthetic fabrics, sealant, grout, compactedearth, low grade shale, or combinations thereof, wherein the controlinfrastructure is formed in direct contact with walls of an excavatedhydrocarbonaceous material deposit or is freestanding having either afoundation support of earthen material or a local surface topography asa floor; b) introducing a comminuted hydrocarbonaceous material into thecontrol infrastructure to form a permeable body of hydrocarbonaceousmaterial; c) heating the permeable body sufficient to removehydrocarbons therefrom such that the hydrocarbonaceous material issubstantially stationary during heating; d) sequestering carbon dioxideproduced during the heating; and e) collecting the removed hydrocarbons.2. The method of claim 1, wherein sequestering carbon dioxide isachieved by reacting carbon dioxide with an aqueous solution to form aprecipitation of carbon dioxide with a metal.
 3. The method of claim 2,wherein the metal is selected from the group consisting of calcium,magnesium, oxides thereof, silicates thereof, and mixtures thereof. 4.The method of claim 2, wherein the aqueous solution is salt water. 5.The method of claim 1, wherein sequestering carbon dioxide is achievedby injecting exhausted hydro carbonaceous materials with the carbondioxide and salt water.
 6. The method of claim 1, wherein sequesteringcarbon dioxide is achieved by cryogenic precipitation forming liquidcarbon dioxide.
 7. The method of claim 6, wherein the liquid carbondioxide is mixed with exhausted hydrocarbonaceous materials.
 8. Themethod of claim 1, wherein sequestering carbon dioxide is achieved byinjecting exhausted hydrocarbonaceous materials with the carbon dioxide.9. The method of claim 8, wherein the injecting is performed with acatalyst.
 10. The method of claim 1, wherein the step of heatingincludes injecting heated gases into the control infrastructure suchthat the permeable body is primarily heated via convection as the heatedgases pass throughout the permeable body.
 11. The method of claim 1,wherein the permeable body further comprises a plurality of conduitsembedded within the permeable body, at least some of said conduits beingconfigured as heating pipes.
 12. The method of claim 1, wherein theinfrastructure comprises clay, bentonite clay, bentonite amended soil,compacted fill, compacted earth, low grade shale, or combinationsthereof.